CN112473666A - Catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method and application thereof - Google Patents
Catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method and application thereof Download PDFInfo
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- CN112473666A CN112473666A CN202011284941.4A CN202011284941A CN112473666A CN 112473666 A CN112473666 A CN 112473666A CN 202011284941 A CN202011284941 A CN 202011284941A CN 112473666 A CN112473666 A CN 112473666A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910016553 CuOx Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 241000894007 species Species 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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Abstract
本发明涉及一种甲醛低温催化氧化用催化剂及其制备方法和应用，该催化剂包括CuOx和活性炭，其中Cu与C的摩尔比为(3.0‑15.0):(85.0‑97.0)，其制备方法包括以下步骤：(1)按摩尔比，将Cu(NO3)2·3H2O溶解后，在搅拌状态下与活性炭混合反应，得到反应液；(2)将反应液升温后，继续搅拌至液体蒸干，得到催化剂；(3)将催化剂干燥、在N2气氛下焙烧。该催化剂应用在甲醛的低温催化氧化中。与现有技术相比，本发明反应温度不高，反应活性高，催化剂制备方法简单，容易放大和产业化。The invention relates to a catalyst for low-temperature catalytic oxidation of formaldehyde and a preparation method and application thereof. The catalyst comprises CuO x and activated carbon, wherein the molar ratio of Cu to C is (3.0-15.0):(85.0-97.0), and the preparation method comprises the following steps: The following steps: (1) after dissolving Cu(NO 3 ) 2 ·3H 2 O in a molar ratio, mix and react with activated carbon in a stirring state to obtain a reaction solution; (2) after heating the reaction solution, continue stirring until the liquid is reached Evaporate to dryness to obtain a catalyst; (3) dry the catalyst and calcinate under N 2 atmosphere. The catalyst is used in the low temperature catalytic oxidation of formaldehyde. Compared with the prior art, the reaction temperature of the invention is not high, the reaction activity is high, the catalyst preparation method is simple, and it is easy to enlarge and industrialize.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a catalyst for low-temperature catalytic oxidation of formaldehyde, and a preparation method and application thereof.
Background
With the excessive pursuit of people for indoor decoration and the use of a large amount of artificial decoration materials, formaldehyde in a closed room can be continuously volatilized and kept at a certain concentration, thereby causing serious threat to human health. Further, since formaldehyde is often wrapped inside the interior of the upholstery material, the volatilization of formaldehyde continues for more than ten years, and thus, effective removal of formaldehyde from the air in the room has been receiving much attention.
The simplest method for eliminating formaldehyde can use a porous material with physical adsorption to adsorb formaldehyde, but because of the limited capacity of the material, the removal efficiency is not good, and the secondary pollution is formed by desorption. The catalytic oxidation method can completely oxidize the formaldehyde into H harmless to human body under mild reaction conditions2O and CO2It becomes the first choice method for removing formaldehyde.
Since the end of the last century, a great deal of work has been carried out at home and abroad on indoor formaldehyde catalytic oxidation reactions and catalytic systems. Among them, the active components of commercial catalysts are generally noble metals (Pt, Au and Pd), and their high price limits their widespread popularization. Co3O4The catalyst has some researches on low-temperature oxidation of CO and formaldehyde oxidation, but the thermal stability and the water resistance of the catalyst are not satisfactory.
The CuO catalyst has low price and stable performance, shows higher catalytic activity in oxidation reactions such as CO oxidation and methanol steam reforming hydrogen production, but in the CO oxidation reaction, a pure oxidation state catalyst is mostly adopted, and a copper state exists in a divalent state, so the reaction temperature is higher.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for low-temperature catalytic oxidation of formaldehyde, which has low reaction temperature and high reaction activity, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a catalyst for low-temp catalytic oxidation of formaldehyde contains CuOxAnd activated carbon, wherein the molar ratio of Cu to C is (3.0-15.0): (85.0-97.0).
Further, the molar ratio of Cu to C is 3.0: 97.0.
Further, the molar ratio of Cu to C is 7.0: 93.0.
Further, the molar ratio of Cu to C is 11.0: 89.0.
Further, the molar ratio of Cu to C is 15.0: 85.0.
A method for preparing the catalyst for the low-temperature catalytic oxidation of formaldehyde, which comprises the following steps:
(1) adding Cu (NO) in a molar ratio3)2·3H2Dissolving O, and mixing with activated carbon under stirring to react to obtain a reaction solution;
(2) heating the reaction solution, and continuously stirring until the liquid is evaporated to dryness to obtain a catalyst;
(3) drying the catalyst in N2And roasting in the atmosphere to obtain the catalyst for low-temperature catalytic oxidation of formaldehyde.
Because the copper component is loaded on the surface of the activated carbon, N is in inert atmosphere2After the catalyst is roasted at 600 ℃, organic micromolecules and C steam can be evaporated from the surface of the activated carbon, so that the copper component can be slowly reduced, oxygen-containing species on the surface of the activated carbon can be gradually reduced, and copper species with high dispersion and low interaction are formed, so that the low-temperature oxidation activity of the catalyst is effectively increased.
Further, the rotation speed of the stirring in the step (1) is 320-; the temperature rise in the step (2) is 58-63 ℃.
Further, the drying temperature in the step (3) is 110-125 ℃, and the drying time is 8-16 h; the roasting temperature is 600-700 ℃, and the roasting time is 1.5-2.5 h.
The application of the catalyst for the low-temperature catalytic oxidation of formaldehyde is disclosed, and the catalyst is applied to the low-temperature catalytic oxidation of formaldehyde.
Further, the catalyst needs to be in N before catalytic oxidation2Pretreating for 20-40min at the temperature of 180 ℃ and 220 ℃ in the atmosphere; the reaction components of the formaldehyde low-temperature catalytic oxidation comprise 600ppm HCHO and 10 vol.% O2And balance gas N2On the contraryThe temperature should be 90-130 ℃. Preferably 120-130 ℃.
The catalyst is in inert atmosphere N2In the next pretreatment process, the activated carbon can slowly reduce copper oxide species, and meanwhile, oxygen-containing species on the surface of the activated carbon can be gradually reduced to form copper species with high dispersion and low interaction, so that the low-temperature oxidation activity of the catalyst is effectively increased.
Compared with the prior art, the Cu/C catalyst adopted by the invention is about 600 ℃, and N is2The high-temperature reduction treatment under the atmosphere can be further characterized by the catalyst, and the oxygen species in the activated carbon are gradually separated out to the surface of the catalyst at the temperature and interact with the copper component to form copper species in a high dispersion state. And some organic small molecules can be evaporated from the surface of the activated carbon, and C steam can further reduce copper species to form rich Cu+And Cu0Species, the presence of which facilitates the dehydrogenation of formaldehyde to form CO, producing CuO with rapid and highly dispersed COxReaction to CO2Thereby remarkably reducing the reaction temperature of the catalyst.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A catalyst for low-temp catalytic oxidation of formaldehyde is prepared through immersing activated carbon in copper nitrate solution, and adding N2The catalyst is prepared by high-temperature reduction activation under the atmosphere, and the composition in the catalyst is calculated according to the molar ratio of copper atoms to carbon contained in the catalyst, and the specific formula is as follows: the preparation method of the Cu/C-3.0/97.0 concrete comprises the following steps:
7.5g of Cu (NO)3)2·3H2Dissolving O in a beaker filled with 26mL of deionized water and a magnetic stirrer, placing the beaker on a magnetic heating stirrer, adjusting the rotating speed of the stirrer to 320-Stirring for 2 hr, adjusting the temperature of the magnetic heating stirrer to 58-63 deg.C, stirring and heating until no liquid is observed, drying the prepared catalyst at 120 deg.C for 12 hr, and adding N2Roasting for 2 hours at 650 ℃ in the atmosphere to obtain the catalyst A for low-temperature catalytic oxidation of formaldehyde.
The catalyst A obtained in the above example and used for catalytic oxidation of HCHO under mild conditions was crushed and sieved out to 20-40 mesh for use.
Activity test of catalyst A for catalytic oxidation of HCHO under mild conditions was conducted in a miniature quartz tube fixed-bed reactor in which 0.5g of catalyst A (40-60 mesh) for catalytic oxidation of HCHO in a room was mixed with an equal volume of quartz sand and fixed to the middle section of a reaction tube (inner diameter 6mm) at N2After pretreatment at 200 ℃ for 30min under an atmosphere (flow rate: 30mL/min), the temperature was lowered to room temperature, and then a reaction gas (content: 600ppm HCHO, 10 vol.% O) was switched2And balance gas N2Total flow rate is 50mL/min), formaldehyde gas is mixed with balance gas N2Flow through a paraformaldehyde bubbler (heated in a water bath at 36 ℃ C.). The reaction temperature is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃, and each temperature point is subjected to online measurement after reaction for 30 min: separating reaction tail gas by carbon molecular sieve chromatographic column, passing through nickel converter, and detecting formaldehyde, CO and CO by FID detector2Respectively recording the HCHO conversion rate and CO corresponding to the detected HCHO under the conditions of reaction temperature of 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 DEG C2The selectivities, the results obtained are shown in the following table:
from the above table it can be seen that the catalyst exhibits a certain catalytic oxidation activity of HCHO at least 90 ℃ and complete catalytic oxidation of HCHO at 130 ℃ and CO2The selectivity is more than 99 percent.
Example 2
A catalyst for low-temp catalytic oxidation of formaldehyde is prepared through immersing activated carbon in copper nitrate solution, and adding N2High under atmosphereThe catalyst is prepared by warm reduction activation, and the composition in the catalyst is calculated according to the molar ratio of copper atoms to carbon contained in the catalyst, and the specific formula is as follows: the preparation method of the Cu/C-7.0/93.0 concrete comprises the following steps:
18.2g of Cu (NO)3)2·3H2Dissolving O in a beaker filled with 63mL of deionized water and a magnetic stirrer, placing the beaker on a magnetic heating stirrer, adjusting the rotating speed of the stirrer to 320-380r/min, adding 10g of activated carbon into the solution after the copper nitrate crystals are completely dissolved, then continuing stirring for 2h, adjusting the temperature of the magnetic heating stirrer to 58-63 ℃, then continuing stirring and heating until no liquid is seen, drying the prepared catalyst at 120 ℃ for 12h, and adding N into the beaker2Roasting for 2 hours at 650 ℃ in the atmosphere to obtain the catalyst B for low-temperature catalytic oxidation of formaldehyde.
The catalyst B obtained in the above example for catalytic oxidation of HCHO under mild conditions was crushed and sieved out to 20-40 mesh for use.
Activity test of catalyst B for catalytic oxidation of HCHO under mild conditions was conducted in a miniature quartz tube fixed-bed reactor in which 0.5g of catalyst B (40-60 mesh) for catalytic oxidation of HCHO in a room was mixed with an equal volume of quartz sand and fixed to the middle section of a reaction tube (inner diameter 6mm) at N2After pretreatment at 200 ℃ for 30min under an atmosphere (flow rate: 30mL/min), the temperature was lowered to room temperature, and then a reaction gas (content: 600ppm HCHO, 10 vol.% O) was switched2And balance gas N2Total flow rate is 50mL/min), formaldehyde gas is mixed with balance gas N2Flow through a paraformaldehyde bubbler (heated in a water bath at 36 ℃ C.). The reaction temperature is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃, and each temperature point is subjected to online measurement after reaction for 30 min: separating reaction tail gas by carbon molecular sieve chromatographic column, passing through nickel converter, and detecting formaldehyde, CO and CO by FID detector2Respectively recording the HCHO conversion rate and CO corresponding to the detected HCHO under the conditions of reaction temperature of 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 DEG C2The selectivities, the results obtained are shown in the following table:
from the above table it can be seen that the catalyst is fully catalytic for HCHO at 120 ℃ and CO2The selectivity reaches 100 percent.
The catalyst B for indoor catalytic oxidation of HCHO obtained in the example was subjected to kinetic activity evaluation, and a micro quartz tube was placed in a reaction furnace at 120 ℃ while maintaining the reaction temperature constant, which corresponds to the conversion of HCHO and CO at different times2The selectivities are given in the following table:
no decrease in activity was observed after 65 hours of continuous operation.
Example 3
A catalyst for low-temp catalytic oxidation of formaldehyde is prepared through immersing activated carbon in copper nitrate solution, and adding N2The catalyst is prepared by high-temperature reduction activation under the atmosphere, and the composition in the catalyst is calculated according to the molar ratio of copper atoms to carbon contained in the catalyst, and the specific formula is as follows: the preparation method of the Cu/C ═ 11.0/89.0 specifically comprises the following steps:
30.0g of Cu (NO)3)2·3H2Dissolving O in a beaker filled with 103mL of deionized water and a magnetic stirrer, placing the beaker on a magnetic heating stirrer, adjusting the rotating speed of the stirrer to 320-380r/min, adding 10g of activated carbon into the solution after the copper nitrate crystals are completely dissolved, then continuously stirring for 2h, adjusting the temperature of the magnetic heating stirrer to 58-63 ℃, then continuously stirring and heating until no liquid is seen, drying the prepared catalyst at 120 ℃ for 12h, and adding N2Roasting for 2 hours at 650 ℃ in the atmosphere to obtain the catalyst C for low-temperature catalytic oxidation of formaldehyde.
The catalyst C obtained in the above example for catalytic oxidation of HCHO under mild conditions was crushed and sieved out to 20-40 mesh for use.
Activity test of catalyst C for catalytic oxidation under mild conditions of HCHO was carried out in a miniature quartz tube fixed bed reactor using 0.5g for indoor HMixing CHO catalytic oxidation catalyst C (40-60 mesh) with equal volume of quartz sand, fixing to the middle section of a reaction tube (inner diameter 6mm) in N2After pretreatment at 200 ℃ for 30min under an atmosphere (flow rate: 30mL/min), the temperature was lowered to room temperature, and then a reaction gas (content: 600ppm HCHO, 10 vol.% O) was switched2And balance gas N2Total flow rate is 50mL/min), formaldehyde gas is mixed with balance gas N2Flow through a paraformaldehyde bubbler (heated in a water bath at 36 ℃ C.). The reaction temperature is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃, and each temperature point is subjected to online measurement after reaction for 30 min: separating reaction tail gas by carbon molecular sieve chromatographic column, passing through nickel converter, and detecting formaldehyde, CO and CO by FID detector2Respectively recording the HCHO conversion rate and CO corresponding to the detected HCHO under the conditions of reaction temperature of 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 DEG C2The selectivities, the results obtained are shown in the following table:
example 4
A catalyst for low-temp catalytic oxidation of formaldehyde is prepared through immersing activated carbon in copper nitrate solution, and adding N2The catalyst is prepared by high-temperature reduction activation under the atmosphere, and the composition in the catalyst is calculated according to the molar ratio of copper atoms to carbon contained in the catalyst, and the specific formula is as follows: the preparation method of the Cu/C-15.0/85.0 concrete comprises the following steps:
42.8g of Cu (NO)3)2·3H2Dissolving O in a beaker filled with 147mL of deionized water and a magnetic stirrer, placing the beaker on a magnetic heating stirrer, adjusting the rotating speed of the stirrer to be 320-380r/min, adding 10g of activated carbon into the solution after the copper nitrate crystals are completely dissolved, then continuously stirring for 2h, adjusting the temperature of the magnetic heating stirrer to be 58-63 ℃, then continuously stirring and heating until no liquid is seen, drying the prepared catalyst for 12h at 120 ℃, and adding N2Roasting for 2 hours at 650 ℃ in the atmosphere to obtain the catalyst D for low-temperature catalytic oxidation of formaldehyde.
The catalyst D obtained in the above example for catalytic oxidation of HCHO under mild conditions was crushed and sieved out to 20-40 mesh for use.
Activity test of catalyst D for catalytic oxidation of HCHO under mild conditions was conducted in a miniature quartz tube fixed-bed reactor in which 0.5g of catalyst D (40-60 mesh) for catalytic oxidation of HCHO in a room was mixed with an equal volume of quartz sand and fixed to the middle section of a reaction tube (inner diameter 6mm) at N2After pretreatment at 200 ℃ for 30min under an atmosphere (flow rate: 30mL/min), the temperature was lowered to room temperature, and then a reaction gas (content: 600ppm HCHO, 10 vol.% O) was switched2And balance gas N2Total flow rate is 50mL/min), formaldehyde gas is mixed with balance gas N2Flow through a paraformaldehyde bubbler (heated in a water bath at 36 ℃ C.). The reaction temperature is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃, and each temperature point is subjected to online measurement after reaction for 30 min: separating reaction tail gas by carbon molecular sieve chromatographic column, passing through nickel converter, and detecting formaldehyde, CO and CO by FID detector2Respectively recording the HCHO conversion rate and CO corresponding to the detected HCHO under the conditions of reaction temperature of 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 DEG C2The selectivities, the results obtained are shown in the following table:
in summary, CuO is usedxthe/C catalyst shows relatively excellent catalytic activity for the low-temperature oxidation of formaldehyde. The catalyst has mild reaction condition, can completely convert formaldehyde at 120 ℃, and has CO2The selectivity of the catalyst is more than 99.8 percent. In addition, the preparation method of the catalyst is simple, and easy to enlarge and industrialize.
Comparative example 1
A catalyst for low-temp catalytic oxidation of formaldehyde is prepared through immersing activated carbon in copper nitrate solution, and adding N2The catalyst is prepared by high-temperature reduction activation under the atmosphere, and the composition in the catalyst is calculated according to the molar ratio of copper atoms to carbon contained in the catalyst, and the specific formula is as follows: the preparation method of the Cu/C-30.0/70.0 concrete comprises the following steps:
86.3g of Cu (NO)3)2·3H2Dissolving O in a beaker filled with 357mL deionized water and a magnetic stirrer, placing the beaker on a magnetic heating stirrer, adjusting the rotating speed of the stirrer to 320-2Roasting for 2 hours at 650 ℃ in the atmosphere to obtain the catalyst E for low-temperature catalytic oxidation of formaldehyde.
The catalyst E obtained in the above example for catalytic oxidation of HCHO under mild conditions was crushed and sieved out to 20-40 mesh for use.
Activity test of catalyst E for catalytic oxidation of HCHO under mild conditions was conducted in a miniature quartz tube fixed-bed reactor in which 0.5g of catalyst E (40-60 mesh) for catalytic oxidation of HCHO in a room was mixed with an equal volume of quartz sand and fixed to the middle section of a reaction tube (inner diameter 6mm) at N2After pretreatment at 200 ℃ for 30min under an atmosphere (flow rate: 30mL/min), the temperature was lowered to room temperature, and then a reaction gas (content: 600ppm HCHO, 10 vol.% O) was switched2And balance gas N2Total flow rate is 50mL/min), formaldehyde gas is mixed with balance gas N2Flow through a paraformaldehyde bubbler (heated in a water bath at 36 ℃ C.). The reaction temperature is 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 ℃, and each temperature point is subjected to online measurement after reaction for 30 min: separating reaction tail gas by carbon molecular sieve chromatographic column, passing through nickel converter, and detecting formaldehyde, CO and CO by FID detector2Respectively recording the HCHO conversion rate and CO corresponding to the detected HCHO under the conditions of reaction temperature of 120 ℃, 140 ℃, 160 ℃, 180 ℃ and 200 DEG C2The selectivities, the results obtained are shown in the following table:
it can be seen from the comparative example that when the copper content is too high, the activity of the catalyst is significantly reduced, the temperature is 200 ℃, the conversion of formaldehyde is close to 100%, and the CO content is slightly higher. The characterization of the catalyst shows that when the copper content is too high, the activated carbon is completely wrapped by the copper, so that the catalyst cannot be fully reduced at 600 ℃ under a nitrogen atmosphere, and the copper oxide particles are seriously aggregated, so that the catalytic performance of the copper oxide is only reflected, and the effect of the activated carbon cannot be reflected.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. The catalyst for low-temperature catalytic oxidation of formaldehyde is characterized by comprising CuOxAnd activated carbon, wherein the molar ratio of Cu to C is (3.0-15.0): (85.0-97.0).
2. The catalyst for the low-temperature catalytic oxidation of formaldehyde according to claim 1, wherein the molar ratio of Cu to C is 3.0: 97.0.
3. The catalyst for the low-temperature catalytic oxidation of formaldehyde according to claim 1, wherein the molar ratio of Cu to C is 7.0: 93.0.
4. The catalyst for the low-temperature catalytic oxidation of formaldehyde according to claim 1, wherein the molar ratio of Cu to C is 11.0: 89.0.
5. The catalyst for the low-temperature catalytic oxidation of formaldehyde according to claim 1, wherein the molar ratio of Cu to C is 15.0: 85.0.
6. A method for preparing the catalyst for the low-temperature catalytic oxidation of formaldehyde according to claim 1, comprising the steps of:
(1) adding Cu (NO) in a molar ratio3)2·3H2Dissolving O, and mixing with activated carbon under stirring to react to obtain a reaction solution;
(2) heating the reaction solution, and continuously stirring until the liquid is evaporated to dryness to obtain a catalyst;
(3) drying the catalyst in N2And roasting in the atmosphere to obtain the catalyst for low-temperature catalytic oxidation of formaldehyde.
7. The method as claimed in claim 6, wherein the stirring speed in step (1) is 320-380r/min for 1-3 h; the temperature rise in the step (2) is 58-63 ℃.
8. The method as claimed in claim 6, wherein the drying temperature in step (3) is 110-125 ℃ and the drying time is 8-16 h; the roasting temperature is 600-700 ℃, and the roasting time is 1.5-2.5 h.
9. Use of a catalyst according to claim 1 for the low-temperature catalytic oxidation of formaldehyde, wherein the catalyst is used in the low-temperature catalytic oxidation of formaldehyde.
10. The use of a catalyst according to claim 9 for the low temperature catalytic oxidation of formaldehyde, wherein the catalyst is required to be N prior to catalytic oxidation2Pretreating for 20-40min at the temperature of 180 ℃ and 220 ℃ in the atmosphere; the reaction components of the formaldehyde low-temperature catalytic oxidation comprise 600ppm HCHO and 10 vol.% O2And balance gas N2The reaction temperature is 90-130℃。
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